Defect chemistry and charge transport in niobium-doped titanium dioxide

The present project has made a comprehensive assessment of the effect of Nb doping on various charge-transfer related properties of TiO2. Of particular focus, the electrical properties of Nb-doped TiO2 (0.65 at %) have been investigated using the simultaneous measurement of electrical conductivity and thermoelectric power. This investigation was undertaken at elevated temperatures (1073 K -- 1298 K) in equilibrium with a gas phase of controlled oxygen activity (10-10 Pa < p(O2) < 75 kPa). In addition, the effect of segregation on the surface versus bulk composition of Nb-doped TiO2 was also investigated at a function of temperature and oxygen activity. Specifically, the following determinations were undertaken: The effect of oxygen activity, p(O2) and temperature on both electrical conductivity and thermoelectric power The effect of Nb on the defect disorder and related electrical properties of TiO2 The determination of equilibration kinetics and the associated chemical diffusion data for Nb-doped TiO2 The determination of Nb bulk diffusion in TiO2 The effect of p(O2), temperature and dopant content on Nb segregation and the related surface composition of Nb-doped TiO2The obtained electrical properties enable the determination of a defect disorder model for Nb-doped TiO2, which may be considered within the following p(O2) regimes: Strongly Reduced Regime. In this regime, the predominant ionic defect was anticipated to be oxygen vacancies compensated electronically by electrons. While the transition to this regime (from higher p(O2)) was clearly observed, the predominant defect disorder existing beyond this transition was not confirmed due to an inability to obtain sufficiently low oxygen activity. Metallic-type conductivity behaviour was observed within this transition region. Reduced Regime I. In this regime, the predominate defect disorder defined by the electronic compensation of incorporated Nb ions by electrons was clearly observed. Reduced Regime II. In this regime, the predominate defect disorder defined by the ionic compensation of incorporated Nb ions by quadruply-charged titanium vacancies, was clearly observed.The present project included the determination of diffusion data which included: Temperature dependence of 93Nb tracer diffusion in single crystal TiO2 over the temperature range 1073 K -- 1573 K Chemical diffusion coefficient over the temperature range 1073 K -- 1298 K and oxygen activity range, 10-10 Pa < p(O2) < 75 kPa These pioneering studies are significant as they enable the prediction of the processing conditions required to reliably 1) incorporate Nb into the TiO2 lattice, and 2) achieve equilibrium with the gas phase.Finally, the present project included investigations on the effect of Nb segregation on the surface composition of Nb-doped TiO2, with the following outcomes: Due to segregation, the surface can be significantly enriched in Nb compared to the bulk The extent of enrichment increases as the bulk Nb content or the oxygen activity is decreased Following enrichment, the surface Nb concentration could be sufficiently high to assume a unique surface phaseThe outcomes of the present project are significant as they can enable the processing of TiO2 with enhanced charge transport and controlled surface properties